Fast Syntheses of MOFs Using Nanosized Zeolite Crystal Seeds In

Subscriber access provided by George Mason University Libraries & VIVA (Virtual Library of Virginia)

Communication

Fast Syntheses of MOFs Using Nanosized Zeolite Crystal Seeds In-situ Generated from Microsized Zeolites Suyan Liu, Ying Zhang, Yan Meng, Fei Gao, Shujing Jiao, and Yangchuan Ke Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/cg301875z • Publication Date (Web): 13 Jun 2013 Downloaded from http://pubs.acs.org on June 21, 2013

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

Crystal Growth & Design is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Crystal Growth & Design

Fast Syntheses of MOFs Using Nanosized Zeolite Crystal Seeds In-situ Generated from Microsized Zeolites Suyan Liu‡, Ying Zhang†,§,*, Yan Meng§, Fei Gao§, Shujing Jiao§ and Yangchuan Ke‡,* †

The State Key Laboratory of Heavy Oil Processing, §Department of Materials Science and Engineering, ‡

Department of Applied Chemistry, China University of Petroleum (Beijing), Changping District, Beijing102249, China

* To whom correspondence should be addressed. E-mail: [email protected]

Corresponding Author: Prof. Dr. Ying Zhang Department of Materials Science and Engineering China University of Petroleum Fuxue Road 18, Changping District Beijing, 102249, China Tel: (+86)10-89732273 Fax: (+86)10-89733200 e-mail: [email protected]

ACS Paragon Plus Environment

1


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 18

ABSTRACT

Herein we report a seeded growth methodology using zeolite crystal seeds for the rapid hydrothermal syntheses of MOFs. Common microsized zeolite crystals without surface modification are added to the hydrothermal synthesis systems of MOFs and break into nanosized zeolite crystal seeds under the MOF hydrothermal synthesis conditions. Nanosized zeolite seeds can offer enormous surface areas to nucleate MOFs and the in-situ generation way can avoid aggregation and separation troubles relevant to nanosized zeolite production. Fast syntheses of MIL-101(Cr), MIL-100(Cr), MIL-104(Co) and MIL53(Fe) were carried out by employing zeolite MOR, Y or ZSM-5 crystal seeds. Typically, only about 1.3 wt% microsized zeolite MOR crystals relative to the metal and ligand precursors for MIL-101 formation can shorten the crystallization complete time by 75% compared to the conventional MIL-101 crystallization without adding zeolites. This nanosized zeolite seed-assisted growth methodology is an important step toward the industrial scale-up of MOF synthesis. Simultaneously, it builds a bridge between MOFs and zeolites, which may shed light on the preparation of composite materials composed of MOFs and zeolites.


2

Page 3 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Zeolites are nanoporous crystalline aluminosilicates that are widely used in the fields of catalysis, separation, ion exchange and sensing.1 Metal-organic frameworks (MOFs) are an emerging class of crystalline nanoporous material constructed from small inorganic clusters connected by multifunctional organic linkers.2-4 As crystalline porous materials, they both possess large internal surface areas, uniform pore and cavity sizes. Meanwhile, MOFs differ from zeolites in that the designability in synthesis and functionalization of organic linkers endow MOFs with rich cavity architectures and diverse functional properties. This makes MOFs have potential applications in gas storage5a and separation,5b catalysis,5c drug delivery5d, optoelectronics5e, sensing5f and in vivo imaging5g under mild conditions. Therefore, for the past decades, much MOFs work has focused on the designable syntheses of novel networks, framework functionalization, property investigation and application exploration of MOFs. However, toward future industrial application on large scale, an important step is developing facile protocols to manipulate MOFs nucleation and growth and finally fabricate MOFs of various desirable forms in an efficient process. In such protocols, rapid synthesis is requisite. For rapid synthesis of MOFs, two common ways, i.e. microwave irradiation and seeded growth, which have been frequently utilized in zeolite quick crystallization, are also employed. Applying microwave-assisted solvothermal synthesis allows high quality MOF crystals to be synthesized in under a minute.6 Through this methodology, a large number of MOFs have been produced efficiently, such as zirconium oxide based Metal–Organic Frameworks6a, IRMOF-1, IRMOF-2, IRMOF-3,6b MIL-101,6c MIL-476d as well as MIL-47 on polymer substrates.6e The seeded growth method has been proved to be a feasible and effective method for the preparation of MOF membranes wherein seeding procedure is a key step.7 Various seeding routes including dip coating, 7a,b,c thermal seeding, 7d,e wiping seeding, 7f reactive seeding7g and step-by-step seeding procedures7h have been developed. Relative to the considerable attention on MOF membranes, the seeded growth of MOF microcrystals is limited.

8

Typically, Falcaro and co-workers have used α-hopeite microparticles as nucleation seeds for growing MOF-5 microcrystals.8a,b This heterogeneous crystallization reduces the MOF-5 synthesis time by 70% when compared with conventional solvothermal methods. They further explore the heterogeneous MOFACS Paragon Plus Environment

3


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 18

5 formation through using SiO2 nanoparticles with tailored surface chemistry as nucleating agents and find that the MOF-5 formation rate is boosted by up to an order of magnitude compared to the conventional solvothermal synthesis.8c We are interested in finding alternative nanosized crystal seeds to stimulate heterogeneous MOF growth, which can be easily obtained and used directly without surface modification. Zeolites are commercially available crystalline materials and zeolite crystal seeds have been widely used to shorten the crystallization time or to improve the quality of zeolite products since the early days.9 However, zeolite crystal seeds have not been employed in the MOF synthesis. Additionally, Okubo and co-workers found that in the beta seed-assisted crystallization process of zeolite beta, the beta seeds in the basic hydrothermal synthesis system were partially dissolved and new beta crystallized on the surface of the residual beta seeds.9a This phenomenon enlightens us to think of the idea that common microsized zeolites are added to in-situ generate nanosized zeolite crystal seeds in the hydrothermal synthesis systems of MOFs. Nanosized seeds can offer enormous surface areas to nucleate MOFs 8c and the in-situ generation way can avoid aggregation and separation troubles relevant to nanosized zeolite production. The success of this nanosized zeolite seed-assisted growth methodology would make important fundamental advances toward the industrial scale-up of MOF synthesis and direct MOF growth on suitable supports for device fabrication. To test the validity of this methodology, MIL-101, one of the hydrothermally synthesized MOFs is chosen. One reason lies in the acidic and high temperature reaction system of MIL-101 will facilitate the degradation of microsized zeolite crystals into nanosized zeolites. Another reason is that MIL-101 is a promising MOF material for industrial application because of the extremely high surface area, large pore volume, and accessible mesopores with free diameters of ca. 2.9 and 3.4 nm as well as high hydrothermal/thermal stability.10 Recent advances in the MIL-101 synthesis focus on HF-free synthesis11 and microwave synthesis6c. Usually, the HF-free synthesis requires longer crystallization time than the conventional HF-containing system. For example, Hatton and co-workers synthesized MIL-101 particles in a Cr(NO3)3-H2BDC-H2O system heated at 218 °C for 18 h.11a Dong et al synthesized MILACS Paragon Plus Environment

4

Page 5 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


101 in a TMAOH-Cr(NO3)3-H2BDC-H2O system heated at 180 °C for 24 h.11b Microwave-assisted hydrothermal synthesis of MIL-101 reported by Ferey et al greatly reduced the crystallization time to 60 min.6c Although the microwave synthesis of MIL-101 shows remarkable formation rates, the zeolite seed-assisted growth of MIL-101 will easily implement an industrial production line since zeolites are cheap and have been industrially produced on a large scale. Again considering the easy degradation, microsized zeolite MOR crystals composed of aggregated rods are selected. The MOR microcrystals are pre-synthesized according to our previous paper

12

and directly added to the hydrothermal synthesis

system of MIL-101 without surface modification. The experimental procedure is as follows: a reaction solution of MIL-101 was produced by mixing 2.67 g Cr(NO3) 3.9H2O, 1.11 g terephthalic acid (H2bdc), 0.45 ml HF(≥ 40 wt%) and 30 ml water, to which 0.05 g MOR microsized crystals were added. The resultant solution was vigorously stirred for 1 h at room temperature, then transferred to a Telfon-lined autoclave and heated at 220 °C for a certain period of time. Green powder products were collected after separation, washed with ethanol and deionized water and dried at a 100 °C oven. For comparison, syntheses from the same reaction solution as above procedure but without MOR crystals were also conducted under the same crystallization conditions. Samples were characterized by PXRD, SEM, EDS, TEM, TG/DSC, FTIR and N2 adsorption techniques. Relative crystallinity was calculated based on the integrated areas of the MIL-101 characteristic PXRD diffraction peaks at 2θ=1.75°, 2.83°, 3.33°, 4.01°, 4.40°, 4.89°, 5.20°, 5.65°, 5.85°, 8.46° and 9.06° using Origin software after baseline correction. To verify the obtainment of nanosized MOR, a control experiment was conducted. 0.05 g microsized MOR crystals were dispersed into 0.45 ml HF (≥ 40 wt%) plus 30 ml water. The suspension was stirred for 1 h and then transferred to a Telfon-lined autoclave and heated at 220 °C for 80 min. After finishing heating, the suspension was deposited on carbon-coated Cu grids for TEM analysis. MOR microcrystals added to the MIL-101 synthesis system exhibit bundles of rods with overall size of 11 µm×12 µm (Figure 1a). After treatment under acidic and high temperature conditions in the ACS Paragon Plus Environment

5


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 6 of 18

control experiment, the MOR microcrystals break into nanorods with size of about 2.5 nm × 20 nm (Figure 1b). The nanorods show obvious crystallinity. Therefore, it is concluded that microsized MOR crystals break into nanosized MOR in the control synthesis. Since the composition and heating temperature in the control synthesis is similar to that for MIL-101 synthesis, the MOR microcrystals are supposed to break into nanosized MOR crystals under the acidic and high temperature conditions for MIL-101 synthesis. The proposed synthesis strategy is shown in Scheme 1. Compared with the conventional MIL-101 synthesis, the MIL-101 synthesis using MOR crystal seeds shows quicker crystallization kinetics (Figure 2C). In the conventional MIL-101 synthesis, the solid product shows very weak PXRD diffraction peaks at 90 min synthesis (Figure 2A). Further increasing crystallization time leads to gradual increase of product crystallinity. At the crystallization time of 510 min, crystallization completes and after that crystallinity decreases rapidly. In contrast, the MIL-101 synthesis using MOR crystal seeds shows strong PXRD diffraction at 90 min (Figure 2B), and after that time crystallinity increases sharply to the maximum at 130 min. Longer crystallization time leads to gradual decrease of product crystallinity. By calculation, we find that adding MOR crystal seeds shortens the crystallization complete time by 75%. The rapid crystallization period is observed to start from 70 min to 130 min. During this period, large quantity of nanosized MOR rods are inferred to generate in-situ from microsized MOR crystals based on the control experiment. These nanorods are thought to serve as nucleation agents and induce fast MIL-101 crystallization nucleation and growth. SEM images (Figure 3) of solid products at different synthesis times give us visual information about the MOR-assisted crystallization process. The edges and corners of large MOR rods (Figure 3a) comprising microsized MOR particles first become smooth (Figure 3b) before they degrade into nanorods. Then the large MOR rods disappear at 80 min and simultaneously MOR nanorods induce spherical particles formation (Figure 3c). PXRD results show such spherical particles are MIL-101 with low crystallinity. Finally, spherical particles evolve into clear-cut submicron-sized MIL-101 octahedral crystals at 130 min (Figure 3e). Further increasing time to 150 min results in the appearance of small


6

Page 7 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


irregular particles (Figure 3f), which is in accordance with the crystallinity decrease shown from the crystallization kinetics curves (Figure 2C). Relative to the well-crystallized MIL-101 sample from the synthesis using MOR crystal seeds at 130 min, the MIL-101 sample with the highest crystallinity in the conventional synthesis only reach a crystallinity degree of 74%. Accordingly, the conventional MIL-101 sample has a BET surface area of 1799 m2.g-1, lower than 2182 m2.g-1 for the MOR-induced sample. Both samples have similar Langmuir surface areas and pore volumes, but the MOR-induced sample has slightly smaller mean pore size probably due to the incorporation of MOR nanorods (Table 1). Compared with the conventional MIL101, in the FTIR spectra of the MOR-induced sample appear additional adsorption peaks at 780 and 940 cm-1 (marked by asterisks in Figure 4), assigned to symmetric T-O-T stretching vibration and asymmetrical stretch of internal tetrahedral derived from MOR structure, respectively.13 TG/DSC (Figure S1, Supporting Information) results show both samples decompose at around 374 °C and exhibit two weight-loss steps as reported in literature: the first occurring in the range 25-250°C relates to the loss of guest water molecules; the second is due to the departure of OH/F groups and the decomposition of the framework between 275 and 400°C.10 However, the second weight loss of the MOR-induced sample is 47.0 %, far less than 63.3% for the conventional MIL-101 sample, due to the corporation of zeolite MOR. Additionally, the amount of zeolite MOR encapsulated in the MIL-101 sample is so small that the PXRD pattern of the MOR-induced MIL-101 sample does not show MOR characteristic diffraction peaks. Despite of the low content of zeolite MOR in the MIL-101 sample, the methodology is possible to be exploited to prepare composite membranes or core-shell materials composed of zeolites and MOFs. EDS surface Cr, O, C, Si, Al element color mapping (Si, Al element mapping in Figure 5 and Cr, O, C element mapping in Figure S2, Supporting Information) of the MOR-induce MIL-101 sample shown in Figure 3e confirms Si and Al elements from MOR nanorods are evenly distributed in the MIL-101 crystals containing Cr, O, C elements. Because of the well dispersion of MOR nanorods, only trace amount of MOR crystals, 1.3 wt% total weight of Cr(NO3) 3.9H2O and H2bdc, can stimulate MIL-101 ACS Paragon Plus Environment

7


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 8 of 18

crystallization dramatically. MOR microcrystals with size smaller than 74µm, 74 µm and 149 µm are used, but the resultant MIL-101 samples almost have the same crystallinity (Figure S3, Supporting Information). This result shows that the morphological size of MOR crystals does not influence the MIL-101 crystallization and that it is MOR nanorods generated from MOR crystals that play an important role in nucleating MIL-101. In addition, the overall Si/Al ratio for the MOR-induced sample is 12 (Figure S4, Supporting Information), higher than the original Si/Al ratio of 5 for the MOR crystals, suggesting Al extraction from MOR crystals in the acid HF synthesis solution. The dealumination of zeolites in acid medium has been widely used in zeolite modification14. To probe the generality of this strategy for other zeolite crystals, conventional ellipsoid zeolite MOR and polyhedron zeolite Y with size of 5 µm×12 µm and about 0.7 µm respectively (Figure S5, Supporting Information) are used for the MIL-101 syntheses at 220 °C for 90 min. Control experiments combined with TEM observation show the conventional zeolite MOR and Y degrade into irregular particles respectively with size of 200-300 nm and 100-200 nm (Figure S6, Supporting Information). The products show MIL-101 PXRD diffraction peaks with similar intensities as that for the MIL-101 sample induced by zeolite MOR with rod morphology (Figure S7, Supporting Information). This suggests that all the zeolites investigated are capable of fostering MIL-101 crystallization by breaking into nanosized counterparts as crystal seeds. Homogenous MIL-101 crystal seeds are also used and the corresponding product shows slightly higher crystallinity than those using zeolites (Figure S7, Supporting Information). Considering the cheap and large scale industrial production of zeolites, zeolite crystals seem superior to MIL-101 crystal seeds. Also to probe the generality of this strategy for other hydrothermally synthesized MOFs, MIL-100(Cr), MIL-104(Co) and MIL-53(Fe) were synthesized by employing zeolite MOR, Y and ZSM-5 crystal seeds respectively. Similar to MIL-101 synthesis, we apply MOR crystals with rod morphology to synthesize MIL-100 at 220 °C (see experimental details in Supporting Information). The PXRD diffraction patterns and crystallization curves (Figure S8, Supporting Information) clearly demonstrate the addition of MOR crystals also can boost the crystallization of MIL-100. Only 3% MOR crystals relative to the solid raw ACS Paragon Plus Environment

8

Page 9 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


materials for MIL-100 formation can shorten the crystallization time from four days to one day. We also synthesized MIL-104(Co) at 180 °C using polyhedron zeolite Y of about 0.5 µm (see experimental details in Supporting Information). Control experiments combined with TEM observation show the submicrosized Y degrade into spheric particles with size of about 3 nm (Figure S9, Supporting Information) under the synthesis conditions for the MIL-104(Co) formation. The addition of 0.4% zeolite Y relative to the solid raw materials can stimulate MIL-104(Co) crystallization process significantly and the crystallization completion time is shortened to 24 h from the conventional time longer than 70 h without adding zeolite Y (see PXRD diffraction patterns and crystallization curves in Figure 6). Again following this strategy, we synthesized MIL-53(Fe) at 150 °C using ZSM-5 rods of about 0.8 µm×10 µm (see experimental details in Supporting Information), which broke into nanoparticles of about 4 nm under the synthesis conditions of MIL-53(Fe) ( Figure S10, Supporting Information). And again, PXRD diffraction patterns and crystallization curves in Figure 7 clearly show the addition of ZSM-5 rods quickens the MIL-53(Fe) crystallization process and the ZSM-5-induced MIL-53(Fe) has higher crystallinity than the conventional MIL-53(Fe) synthesized for the same crystallization time. Therefore, this seeded growth methodology using zeolite crystal seeds may serve as a general method for the rapid hydrothermal syntheses of MOFs. In summary, we report a method for the rapid synthesis of MOFs crystals using nanosized zeolite crystal seeds for the first time. To exemplify such method, MIL-101(Cr), MIL-100(Cr), MIL-104(Co) and MIL-53(Fe) were synthesized by employing zeolite MOR, Y or ZSM-5 nanosized crystal seeds. The nanosized zeolite crystal seeds are in-situ generated from microsized zeolites under the MOF synthesis conditions. During synthesis process, microsized zeolites are simply added to the MOF hydrothermal synthesis system without any modification. Only trace amount of zeolite crystals can produce enough nanosized zeolite seeds to shorten the MOFs’ crystallization times significantly. The concept of directly adding cheap zeolite crystals to stimulate MOFs growth provides a facile method for quick production of MOFs in large scale. It also builds a bridge between MOFs and zeolites. The preparation of


9


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 10 of 18

composite materials with core-shell structures or composite membranes composed of MOFs and zeolites are underway. These composites may find special applications in gas separation and catalysis.

Acknowledgment.

We acknowledge the support of this work by the National Natural Science

Foundation of China (Grant No. 51072230, U1162118), the Scientific Research Foundation of the Education Ministry for Returned Chinese Scholars and the Scientific Research Foundation of China University of Petroleum, Beijing (01JB0149). We also thank Microstructure Laboratory for Energy Materials for SEM characterization. Supporting Information Available: Characterization techniques, more experimental details and characterization results. This material is available free of charge via the Internet at http://pubs.acs.org. References (1) Introduction to Zeolite Science and Practice;Van Bekkum, H., Flanigen, E. M., Jacobs, P. A., Jansen, J. C., Eds.; Elsevier: the Netherlands, 2001; Vol. 137, pp 1-1062. (2) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.; O’Keeffe, M.; Yaghi, O. M. Science 2002, 295, 469–472. (3) Eddaoudi, M.; Moler, D. B.; Li, H. L.; Chen, B. L.; Reineke, T. M.; O’Keeffe, M.; Yaghi, O. M. Acc. Chem. Res. 2001, 34, 319–330. (4) Férey, G. Chem. Soc. Rev. 2008, 37, 191–214. (5) (a) Murray, L. J.; Dincă, M.; Long, J. R. Chem. Soc. Rev. 2009, 38, 1294–1314. (b) Alaerts, L.; Kirschhock, C. E. A.; Maes, M.; Van Der Veen, M. A.; Finsy, V.; Depla, A.; Martens, J. A.; Baron, G. V.; Jacobs, P. A.; Denayer, J. E. M.; De Vos, D. E. Angew. Chem. Int. Ed. 2007, 46, 4293–4297. (c) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp, J. T. Chem. Soc. Rev. 2009, 38, 1450–1459. (d) Horcajada, P.; Chalati, T.; Serre, C.; Gillet, B.; Sebrie, C.; Baati, T.; Eubank, J. F.; Heurtaux, D.; Clayette, P.; Kreuz, C.; Chang, J. S.; Hwang, Y. K.; Marsaud, V.; Bories, P. N.; Cynober, L.; Gil, S.; Férey, G.; Couvreur, P.; Gref, R. Nat. Mater. ACS Paragon Plus Environment

10

Page 11 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


2010, 9, 172–178. (e) Winston, E. B.; Lowell, P. J.; Vacek, J.; Chocholousova, J.; Michl, J.; Price, J. C. Phys. Chem. Chem. Phys. 2008, 10, 5188–5191. (f) Lin, W.; Rieter, W. J.; Taylor, K. M. L. Angew. Chem., Int. Ed. 2009, 48, 650–658. (g) Taylor, K. M. L.; Rieter, W. J.; Lin, W. J. Am. Chem. Soc. 2008, 130, 14358–14359. (6) (a) Yoo, Y.; Jeong, H. K. Chem. Commun. 2008, 21, 2441–2443. (b) Ni, Z.; Masel, R. I. J. Am. Chem. Soc. 2006, 128(38), 12394–12395. (c) Jhung, S. H.; Lee, J. H.; Yoon, J. W.; Serre, C.; Férey, G.; Chang, J. S. Adv. Mater. 2007, 19, 121−124. (d) Centrone, A.; Harada, T.; Speakman, S.; Hatton, T. A. Small 2010, 6(15), 1598–1602. (e) Centrone, A.; Yang, Y.; Speakman, S.; Bromberg, L.; Rutledge, G. C.; Hatton, T. A. J. Am. Chem. Soc. 2010, 132(44), 15687–15691. (7) (a) Demessence, A.; Horcajada, P.; Serre, C.; Boissiere, C.; Grosso, D.; Sanchez, C.; Férey, G. Chem. Commun. 2009, 0, 7149−7151. (b) Horcajada, P.; Serre, C.; Grosso, D.; Boissière, C.; Perruchas, S.; Sanchez, C.; Férey, G. Adv. Mater. 2009, 21(19), 1931−1935. (c) Li, Y. S.; Liang, F. Y.; Bux, H.; Feldhoff, A.; Yang, W. S.; Caro, J. Angew. Chem. Int. Ed. 2010, 49, 548–551. (d) Ranjan, R.; Tsapatsis, M. Chem. Mater. 2009, 21, 4920−4924. (e) Guerrero, V. V.; Yoo, Y.; McCarthy, M. C.; Jeong, H. K. J. Mater. Chem. 2010, 20, 3938–3943. (f) Venna, S. R.; Carreon, M. A. J. Am. Chem. Soc. 2010, 132(1), 76–78. (g) Hu, Y.; Dong, X.; Nan, J.; Jin, W.; Ren, X.; Xu, N.; Lee, Y. M. Chem. Commun. 2011, 47, 737–739. (h) Nan, J.; Dong, X.; Wang, W.; Jin, W.; Xu, N. Langmuir 2011, 27, 4309–4312. (8) (a) Falcaro, P.; Hill, A. J.; Nairn, K. M.; Jasieniak, J.; Mardel, J. I.; Bastow, T. J.; Mayo, S. C.; Gimona, M.; Gomez, D.; Whitfield, H. J.; Riccò, R.; Patelli, A.; Marmiroli, B.; Amenitsch, H.; Colson, T.; Villanova, L.; Buso, D.; Nat. Commun. 2011, 2, 1−8. (b) Buso, D.; Hill, A. J.; Colson, T.; Whitfield, H. J.; Patelli, A.; Scopece, P.; Doherty, C. M.; Falcaro, P. Cryst. Growth Des. 2011, 11, 5268–5274. (c) Buso, D.; Nairn, K. M.; Gimona, M.; Hill, A. J.; Falcaro, P. Chem. Mater. 2011, 23, 929–934. (9) (a) Kamimura, Y.; Tanahashi, S.; Itabashi, K.; Shimojima, A.; Okubo, T. J. Phys. Chem. C 2011, 115, 744−750. (b) Itabashi, K.; Kamimura, Y.; Iyoki, K.; Shimojima, A.; Okubo, T. J. Am. Chem. ACS Paragon Plus Environment

11


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 12 of 18

Soc. 2012, 134, 11542−11549. (c) Xie, B.; Zhang, H.; Yang, C.; Liu, S.; Ren, L.; Zhang, L.; Meng, X.; Yilmaz, B.; Müller, U.; Xiao, F. S. Chem. Commun. 2011, 47, 3945−3947. (d) Yokoi, T.; Yoshioka, M.; Imai, H.; Tatsumi, T. Angew. Chem. Int. Ed. 2009, 48, 9884−9887. (e) Kerr, G. T. J. Phys. Chem. 1968, 72, 1385−1386. (f) Edelman, R. D.; Kudalkar, D. V.; Ong, T.; Warzywoda, J.; Thompson, R. W. Zeolites 1989, 9, 496−502. (g) Gora, L.; Streletzky, K.; Thompson, R. W.; Phillies, G. D. J. Zeolites 1997, 19, 98−106. (10) Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange, F.; Dutour, J.; Surblé, S.; Margiolaki, I. Science 2005, 309, 2040−2042. (11) (a) Bromberg, L.; Diao,Y.; Wu, H.; Speakman, S. A.; Hatton, T. A. Chem. Mater. 2012, 24, 1664−1675. (b) Yang, J.; Zhao, Q.; Li , J.; Dong, J. Micropor. Mesopor. Mater. 2010, 130, 174– 179. (12) Liu, S.; Gong, Y.; Yang, K.; Piao, J.; Dou, T. Acta Petro. Sin. 2008, 24, 131-135. (13) Sharma, P.; Rajaramb, P.; Tomar, R. J. Colloid Interface Sci. 2008, 325, 547–557. (14) (a) Matias, P.; Lopes, J. M.; Ayrault, P.; Laforge, S.; Magnoux, P.; Guisnet, M.; Ribeiro, F. R. Appl. Catal. A 2009, 365(2), 207–213. (b) Kooyman, P. J.; Van der Waal, P.; Van Bekkum, H. Zeolites 1997, 18, 50–53. (c) Baran, R.; Millot, Y.; Onfroy, T.; Krafft, J. M.; Dzwigaj, S. Micropor. Mesopor. Mater. 2012, 163, 122–130.


12

Page 13 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


For Table of Contents Use Only: Fast Syntheses of MOFs Using Nanosized Zeolite Crystal Seeds In-situ Generated from Microsized Zeolites Suyan Liu, Ying Zhang*, Yan Meng, Fei Gao, Shujing Jiao and Yangchuan Ke*

Common microsized zeolite crystals without surface modification have been added to the hydrothermal synthesis systems of MOFs and break into nanosized zeolite crystal seeds with enormous surface areas to stimulate MOFs growth. The nanosized zeolite seed-assisted growth methodology is an important step toward the MOFs industrial production and may shed light on the preparation of MOFs and zeolites composite materials.


13


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 14 of 18

a

b

Scheme 1 Synthesis strategies of (a) MIL-101 crystals using zeolite MOR nanorods in-situ generated from microsized zeolite MOR and (b) the control experiment wherein microsized zeolite MOR break into MOR nanorods.

Table 1. The pore parameters of two MIL-101 samples. Samples

SBET/(m2.g-1)

SLangmuir/ (m2.g-1)

Pore volume/ (cm3.g-1)

Pore size/nm

The conventional MIL-101 sample

1799

3058

1.03

2.29

The MORinduced MIL101 sample

2182

2916

1.00

2.01


14

Page 15 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figures Captions

Figure 1 SEM image of (a) microsized MOR and TEM image of (b) the nanorods generated from the microsized MOR.

Figure 2 PXRD patterns of the MIL-101 samples synthesized (A) in the conventional systems and (B) using MOR crystal seeds at different times and the crystallization kinetics curves (C) of (a) the conventional and (b) MOR-induced MIL-101 syntheses.

Figure 3 SEM images of MIL-101 samples synthesized using MOR crystal seeds at (a) 50 min, (b) 70 min, (c) 80 min, (d) 90 min, (e) 130min and (f) 150 min.

Figure 4 FTIR spectra of (a) the MOR-induce MIL-101 sample, (b) the conventional MIL-101 sample and (c) microsized MOR.

Figure 5 EDS surface chemical mapping of the MOR-induce MIL-101 sample with the SEM image shown in Fig.3e: (a) Si element yellow mapping; (b) Al element blue mapping.

Figure 6 PXRD patterns of the MIL-104 samples synthesized (A) in the conventional systems and (B) using zeolite Y crystal seeds at different times and the crystallization kinetics curves (C) of (a) the conventional and (b) zeolite Y-induced MIL-104 syntheses.

Figure 7 PXRD patterns of the MIL-53 samples synthesized (A) in the conventional systems and (B) using zeolite ZSM-5 crystal seeds at different times and the crystallization kinetics curves (C) of (a) the conventional and (b) zeolite ZSM-5-induced MIL-53 syntheses.


15


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

b

a

2 µm

Page 16 of 18

5 nm

Figure 1

Figure 2

b

a

5 µm

10 µm

1 µm

d

1 µm

c

e

1 µm

f

1 µm

Figure 3


16

Page 17 of 18

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


Figure 4 a

b

Figure 5

Figure 6


17


1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 18 of 18

Figure 7


18

Fast Syntheses of MOFs Using Nanosized Zeolite Crystal Seeds In

Recommend Documents